Heterocyclic mercury amine compounds



Patented Feb. 2, 1954 HETEROCYGLIC MERGURY AMINE COMPOUNDS Frank J. Sowa, Cranford, N. J

No Drawing.- Application September 18, 1950, Serial No. 185,508

8 Claims. (01. 2so .z70)

application is a continuation-in-part of (impending application Serial No. 757,953, filed June 28., 1947, now Patent No. 2,524,547.

In applicants issued Patent No. 2,423,262 dated July 1, 1947., there are described methods and products wherein aromatic and heterocyclic mercury compounds are reacted with alkanol amines to produce compounds wherein a mercury group and an anion are bonded to the nitrogen of the amines by the latent valenoes of the atom so that a quaternary ammonium type compound is produced. It is pointedout in said patent that when the amine employed is itself water soluble and also is hydroxylated the resulting reaction products are water soluble.

In the foregoing err-pending, application amine addition products are produced by reactions between aromatic mercury'compounds and amines which are not hydroxy lated and do not contain any hydroxylated substituentsf In accordance with the present invention heterocyclic mercury compounds are reacted with primary amines which are not hydrox-ylated and which do not contain hydroxylated substitu-' ents. It is found that such heterocyclic com pounds are of a quaternary type and are'gen orally soluble in both water and organic solvents. The products of the present invention are generally characterized by their bacteriocidal and fungicidal properties rendering them useful as agricultural sprays and for addition to paints, coating compositions, soaps and for pharmaceutical purposes and slime control.

One of the objects of the present invention is to provide a novel heterocyclic mercury containing fungicidal compound of a quaternary type.

Another object of the invention is to provide novel methods for producing new fungicidal com- Bounds.

A particular object ofthe invention is to provide new fungicidal compounds by reaction between the heterocyclic mercury-compound and a primary amine which contains no hydroxylated substituents.

These and other objects and features of the invention will appear from the following description thereof.

. The organic mercury compounds employed in the practice -.of the present invention have the general formula R-Hg-X in which R is a heterocyclic group and X is an anion. These compounds diiTer markedly from aliphatic and alicyclic compounds and from inorganic mercury compounds in that they are themselves generally less corrosive to the skin and easier to employ and they result in the formation of reaction products which are not so injurious or toxic to plant and animal life. Moreover, many inorganic compounds cannot be used to produce stable or satisfactory reaction prodnets with amines. Furthermore, when it is desired to produce reaction products which are more soluble in water and common solvents the anion of the R-Hg-X compound should be-an organic acid radical or a .hydroxyl group.

The products produced whenemploying heterocyclic mercury compound-s rather than aryl mercury compounds vare characterized by the fact that they are more effective against certain types of organisms and are even less irritating to the skin than the aromatic compounds.

Typical heterocyclic compounds which may be used in the practice of the present invention are pyridyl mercuric acetate, '2-methyl-5-acetoxymercuricthiophene, 2,-5-diacetoxymercuric-thio phone, 2emethyle5-acetoxymercuric-duran. However, these compounds are only cited as typical of those which maybe employed, since I believethe reaction to be generic in that all compounds having the general formula mal octyl amine, lauryl amine, myristyl amine,

decyl amine, cetyl amine and stearyl amine. It has also been found that branch chain amines such as Z-amino heptane can be used. Among the alicyclic amines which may be employed are cyclohexylamine, ortho amino dicyclohexyl. Airalkyl amines such as benzyl amine and unsatu-= rated alkyl amines such as oleyl amine and octa decenylamine maybe used also. However, numerous other amines may be employed since it appears that the reaction is and may be amine. V

The reaction by which the new products are carried out when using any primary produced may be expressed by the following em pirical equation generic in character 3 wherein R is a heterocyclic group and X is an anion, and R1 is a hydrocarbon radical.

Products of such reactions wherein the amine employed is an aliphatic amine containing from 6 to 18 carbon atoms possess the properties of a wetting agent and those containing 8 or more carbon atoms also have detergent properties. A striking characteristic of those reaction products wherein long chain aliphatic amines are used resides in the fact that the addition of the organic mercury group to the amine serves in most instances to result in increased water olubility. Thus for example lauryl amine, which is substantially insoluble in water, may be combined with pyridyl mercuric acetate and similar compounds to produce reactionproductswhich are readily soluble in water. The reaction products of the present invention are generally also soluble in ethanol, hydrocarbons and organic solvents. They are further characteried by their fungicidal action which render them particularly suitable for use in sprays, for agricultural and other purposes, in textile treatment, and in soaps, paints, lacquers, coating compositions, plastics and cork compositions and for many other purposes wherein the fungicidal and bactericidal properties of the compound are desired or necessary. Their use in pharmaceutical preparations shows considerable promise.

In general the amines used in the practice of the present invention contain at least 6 carbon atoms, since it is found that those products wherein the lower alkyl amines are used are ordinarily much less stable and tend to decompose on standing with the separation of the amine.

The reaction by which the new fungicidal compounds are produced are preferably conducted at ordinary room temperatures and pressures, al though the reaction mixture may be heated if desired and in many instances the reaction is exothermic producing a spontaneous rise in temperature as the reaction proceeds. The reaction is usually carried out in the presence of an organic solvent such as ethanol and may be conducted by simply dissolving the reactants in ethanol or by otherwise mixing the organic mercury compound with theamine in the presence of an organic solvent. The temperature of the reaction is preferably maintained below the boiling point of the solvent employed.

In order to indicate the nature of my invention more fully and to illustrate typical procedure and products to which my invention relates, the following examples are cited:

In the following examples the pyridyl-mercuric acetate used was a commercial product which according to the manufacturer is assayed at about 75% pyridyl mercuric acetate, the rest being alkali acetates. Accordingly in the examples allowance is made for the impurities using 41 grams pyridyl mercuric acetate, containing 30.7 grams (0.0935 mol.) of the mercurial. In all cases 0.1 mol of amine was used. The long chain amines employed were commercial materials.

Ezmmple 1 To 41 g. of pyridylmercuric acetate were added 100 cc. of benzene and 18.5 g. of laurylamine. Immediate reaction occurred upon stirring the materials and a major portion of the solid went into solution. After one half hour of stirring the product was filtered. The benzen was evaporated and there was obtained a viscous oil which solidified upon standing overnight. The yield was 44.5 g. The crude product was pale yellow in color and melted at 40-41 C. After a thorough washing with ethyl ether the pure white crystalline material obtained melted at 46-47" C. This product is believed to have the following structural formula:

Hg NC12H2s I O \N 00 cm This product may be termed pyridyl mercuri lauryl ammonium acetate.

Example 2 To 41 g. of pyridyl mercuric acetate were added l25 cc. of benzene and 21.3 g. myristyl amine. Im-

mediate reaction occurred upon stirring the materials and a major portion of the mercurial went into solution. After standing for three hours the product was filtered and the benzene evaporated yielding a viscous oil which upon standing overnight solidified to a pale orange solid melting at 36-37 C. The yield was 49 g. After thorough washing with ethyl ether the pure white material obtained melted at 47-48" C. This product is believed to have the following structural formula:

This product may be be termed pyridyl mercuri myristyl ammonium acetate.

Example 3 \N o oom This product may b termed pyridyl mercuri cetyl ammonium acetate.

Example 4 To 41 g. of pyridyl mercuric acetate were added cc. of benzene and 26.9 g. of stearyl amine. Immediate reaction occurred upon stirring and the major portion of the mercurial ultimately went into solution. After stirring for three hours the product was filtered and the benzene evaporated leaving a pale yellow solid which melted at 49-50 C. The yield was 42 g. After washing with ethyl other the pure white crystalline product obtained melted at 52.5-53.5 C. This prodnot is believed to have the following structural formula:

0 O-G-CHr This product may be termed pyridyl mercuri stearyl'ammonium acetate. I

Example 5 This product may be termed pyridyl mercuri octyl ammonium acetate.

Example 6 To 4 g. of pyridyl mercuric acetate were added 125 cc. of benzene and 10.7 g. of benzyl amine. A rapid reaction occurred and the mixture became slightly warm. After stirring for three hours the product was allowed to settle and separated into two layers. in color and weighed 29 g. The product is believed to have the following structural formula:

This product may be termed pyridyl mercuri benzyl ammonium acetate.

Eridmple 7 To 41 g. of pyridyl mercuric acetate were added 125 cc. of benzene and 9.9 g. of cyclohexylamine. A rapid reaction occurred and the mixture became slightly Warm. After two and. one half hours of stirring the product was allowed to settle and separated into two layers. The lower layer solidified upon standing and the benzene was decanted. The yield was 47 g. However, the product was impure by reason of the presence of alkali acetates which would not separate from the amine complex even when extracted with isopropyl alcohol, acetone, dioxane, ethyl acetate, and cyclohexane. have the following structural formula:

This product may be termed pyridyl mercuri cyclohexyl ammonium acetate.

Example 8 To 35.7 g. of 2-methyl 5-acetoxymercuricthiophene were added 75 cc. of ethanol. While this mixture was stirred 'a solution of 18.5 g. of

lauryl amine in 25 cc. of ethanol was added. A

rapid exothermic reaction occurred and solution of the mercurial was quickly effected. Within a The lower oilier layer was orange This product is believed to yielding a yellow oil weighing 48 g. This product is believed'to have the following structural formula o-c om v This product may be termed 2 methyl 5 mercuri thienyl lauryl ammonium acetate.

Example 9 To 35.7 g. of 2-methy1-5-acetoxymerouricthiophene was added 100 cc. of ethanol. While this mixture was stirred a solution of 24.1 g. of cetyl amine and 50 cc. of ethanol were added. A rapid reaction occurred and most of the mercurial went into solution. After 45 minutes of stirring the product was filtered. The filtrate was evaporated yielding 56.5 g. of a pale yellow solid which melted at 4041 C. This product is believed to have the following structural formula:

co om This product may be termed 2 methyl 5 mercuri thienyl cetyl ammonium acetate.

Example 10 To 35.7 g. of 2-methyl-5-acetoxymercuricthiophene was added 100 cc. of ethanol and while the mixture was stirred a solution of 26.9 g. of

stearyl amine and 50 cc. of ethanol were added.

A rapid reaction occurred and most of the mercurial went into solution. After stirring for three hours the product was filtered. The ethanol was evaporated from the filtrate leaving a pale yellow solid melting at 485,0 C. This product is believed to have the following structural formula:

This product may be termed 2 methyl 5 mercuri thienyl stearyl ammonium acetate.

Example 11 product was filtered and the filtrate evaporated yielding 42.5 g. of a viscous pale yellow oil. This product is believed to have the following structural formula:

This product may be termed 2 methyl 5 mercuri thienyl octyl ammonium acetate.

Each of the foregoing examples was repeated using isopropyl and butyl amine whereupon an I claim: Y 1. A fungicidal compound having the composition represented by the formula R-Hg R1 x H wherein R is a heterocyclic radical selected from the group consisting of pyridyl, thienyl, and furyl radicals, X is an anion, and R1 is a hydrocarbon radical selected from the group consisting of alkyl radicals containing 6 to 18 carbon Example Cyclo- Stoddard Solox Ethy No. Benzene Acetone hexane Solvent (Ethanol) Acetate wabel v.sol. v.s1.sol sol sLsol v. 501.... sol sol 31. so! v.sol.. sol s1. sol soLwarm... o1 soLwarm-..

v.sol. v. sol v. 501.."

No'rE.v.=vcry; sol. =soluble; sl. =slightly.

Solutions wherein the reaction products of the present invention are dissolved in water or organic solvents may be employed as fungicidal sprays for agricultural purposes, for the treat- 30 ment of textile fabrics, and for other uses, and the reaction products may be added to paints, lacquers, varnishes and other coating compositions which embody an organic solvent. They also may be employed as constituents of molded 35 or plastic compositions or filaments or sheets of plastic material.

While I have indicated preferred procedure for use in producing products of my invention and have cited numerous examples of these new 40 fungicidal compounds, it will be apparent that many other methods and compositions may be produced and used in accordance with my invention. Therefore, it should be understood that the methods and examples particularly described 45 above are intended to be illustrative only and are not intended to limit the scope of my invention.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,085,065 Andersen June 29, 1937 2,423,121 Sowa July 1, 1947 2,423,262 Sowa July 1. 1947 2,524,547 Sowa Oct. 3, 1950 

1. A FUNGICIDAL COMPOUND HAVING THE COMPOSITION REPRESENTED BY THE FORMULA 